Organic amine-organic acid addition salts

ABSTRACT

Organic amine-organic acid addition salts are employed in compositions for topical application to a human being having a scalp or skin characterized by an excessive secretion of sebum to improve the condition of the scalp or skin by reducing said excessive secretion.

United States Patent Kalopissis 51 Apr. 22, 1975 ORGANIC AMlNE-ORGANICACID ADDITION SALTS TO REDUCE EXCESSIVE SECRETION OF SEBAM ON HUMAN SKINAND SCALP lnventor:

Assignee:

Gregoire Kalopissis, Paris. France Societe Anonyme dite: LOreal.

Paris. France Filed:

Nov. 29, 1971 Appl. No.: 203.038

Related US. Application Data Continuation-impart of Ser. No. 801.840.Feb. 24. 1969. abandoned. and a continuation-in-part of Scr. No.858.161. Sept. 15. 1969. Pat. No. 3.671.643.

Foreign Application Priority Data 260/534 S; 260/501.21; 260/534 E;260/570.5 S; 260/534 G; 260/583 EE; 424/D1G. 1; 424/D1G. 2; 424/D1G. 4;

260/11; 260/247.l; 260/268 C; 260/294.8 R; 260/329; 260/332.2;260/349.2; 260/390; 260/501.12; 260/501.16

[51] int. Cl A61k 27/00 [58] Field of Search 260/501.12. 501.21. 501.2;

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 1.085.513 7/1954France 260/501.12

Primary E.\'uminerA1bert T. Meyer Assistant E.\aminerVera C. ClarkeAttorney. Agent. or FirmCushman. Darby & Cushman 57 ABSTRACT Organicamine-organic acid addition salts are employed in compositions fortopical application to a human being having a scalp or skincharacterized by an excessive secretion of sebum to improve thecondition of the scalp or skin by reducing said excessive secretion.

-4 Claims, No Drawings ORGANIC AMINE-ORGANIC ACID ADDITION SALTS TOREDUCE EXCESSIVE SECRETION OF SERUM ON HUMAN SKIN AND SCALP Thisapplication is a continuation-in-part of my earlier applications Ser.No. 801,840, filed Feb. 24, 1969, now abandoned; Ser. No. 858,161, filedSept. 15, 1969, now US. Pat. No. 3,671,643, which in turn discloses andclaims subject matter of my application Ser. No. 801,840, supra, Ser.No. 817,193, filed Apr. 17, 1969, now abandoned, and Ser. No. 736,960,filed June 14, 1968, now abandoned, which in turn discloses and claimssubject matter of my applications Ser. No. 602,480, filed Dec. 19, 1966,now abandoned, and Ser. No. 427,976, filed Jan. 25, 1965, now abandoned;Ser. No. 12,122, filed Feb. 17, 1970, now abandoned; and Ser. No.36,405, filed May 11, 1970, now abandoned.

This invention relates to compounds usefully employed in compositionswhich, when administered orally or topically to a human being having ascalp or skin characterized by an excessive secretion of sebum, improvesthe condition of the scalp or skin by reducing said excessive secretion.The compounds of this invention are water-soluble salts and havethefollowing formula wherein n is or 1 and when n is 0, R, and R areselected from the group consisting of hydrogen and CH and when n is 1, Rand R are hydrogen ,R is selected (CHQ R wherein z is O, 1 or 2 and whenz is 0, R915 selected from the group consisting of naphthyll,naphthyl-2, pyridyl-2, pyridyl-2 substituted with a wherein x is 0-2 andwherein when q is 1, 2 or 3, R is selected from the group consisting ofhydrogen, halogen such as chlorine or bromine, alkoxy having l-5 S-CH -Ycarbon atoms, linear or branched alkyl having l-4 carbon atoms and whenq is LR is selected from the group consisting of acetamido, amino,phenoxy, cyclofrom the group consisting of R;, and R";,, R;; is sehexyl,methylenedioxy, trifluoromethyl, nitro, phenyl,

lected from the group consisting of linear or branched alkyl having 1-l8carbon atoms, alkenyl having 3-18 carbon atoms, propyne-2 yl, mono ordihydroxy alkyl containing 2-4 carbon atoms, 1-2 dichloro-vinyl, C (C HCO NH CH (C H CH (C H p a)2 C (CH3)2 (C6H4 1 a),

/OR' (CH on wherein R is alkyl having 1-4 carbon atoms and m is (ca c /0B wherein m is 1-2 and B is selected from the group consisting of CH CHand "CH-CH dialkylamino, alkylthio, alkylsulfinyl and alkylsulfonylwherein each alkyl moiety has 1-5 carbon atoms,

- CH2 (cs pa NI-l COOH - cs (C1-I CH NHA wherein n is O or 1,

R is selected from the group consisting of hydrogen and COR wherein R isselected from the group consisting of alkoxy having 1-5 carbon atoms,glucosamino, NH NH NHOH, -O CH -CH-CH wherein r is selected from thegroup consisting of hydrogen and alkyl having l-3 carbon atoms,

- o (CI-[2J2 N wherein R has the meaning given above; R" has the havingl-l8 carbon atoms, alkenyl having 2-18 carbon 10 ormu a:

atoms, CH Cl, CP

a CH cl: CH2 OH 0H CH CH2 CH2 NH-CO -CHOH- p CH2 OH 8 CH2 CH2 coon, and(CI-{Q0 25 wherein n, R, and R have the same meaning as above given andR is selected from the group consisting of alkylene having 2-4 carbonatoms, alkylene having 2-4 carbon atoms and substituted with 1-2 hydroxygroups, butylene and (CH S0 (Cl-l Y is selected from the groupconsisting of (a) ICH CO H in which case R represents (CH COOH" whereineis l 5and (b) CH COOH wherein A' has the same meaning given NHA' 'except that in the value of R' as CH2 (CH2 cpl NH A is other thanhydrogen,

(CH COOH wherein s is n have l-5, CH (Cl-2 (IIH COOH wherein A l andhave the meanings given above,and

wherein p is O l and R is selected from the group consisting ofhydrogen, alkyl having 1-4 carbon atoms, alkoxy having 1-4 carbon atoms,halogen and acetwherein A, and R have the meanings given above,

andxislor2andwislor2.

Representative of such active compounds Wl'llCll can amido and wherein 1is Selected from the g p 65 be utilized in the compositions of thisinvention are set sisting of alkyl having 1-4 carbon atoms and forth inTable 1, below:

-' s CH2 CH coon 16.7 g of Z-benzylthio ethylamine are introduced in Theresulting compound is a white solid melting at a 250 Cm" flask equippedWith a reflux Condenser an 186C. It is soluble in water but insoluble inalcohols.

containing a suspension of 17.9 g of S-carboxy-methyll-cysteine in 95 cmof tetrahydrofuran, while the mix- EXAMPLE 4 ture is being agitated- 5Preparation of 5-amino-3-thia hexanedioate of The mixture is heated tothe boiling point of the sol- 2 methylthio ethylammonium having theformula;

vent and water is then added drop by drop until a vigorous exothermicreaction is initiated, which is followed by the formation of solids inthe reaction mixture. This is left to stand overnight at lOC. Q Q

After filtration, the precipitate is rinsed in tetrahydrofuran, then inacetone, drained and vacuum dried at 2 The result is 31.2 g of5-amino-3-thia hexanedioate H2NCHZ'CHTS'CHK of2-benzylthio-ethylammonium. In the same manner as in Example 3, 9 g ofS-carbox- This ompoun elts at 6- ymethyl-cysteine are reacted with 5 gof 2-methylthi0e- Analysis reveals that it contains y Weight ofthylamine. This reaction is carried out in ethanol.

sulfur, the theoretical percentage of sulfur being 18.55 The resultingproduct is a white Solid melting at The resulting compound is insolublein alcohols and 20 conventional organic solvents even when hot. On theother hand, it is very soluble in water and in an aqueous lower alkanolmedium. EXAMPLE 5 EXAMPLE 2 Preparation of 5-amino-3-thia hexanedioateof Preparation of 5-acetamido-3-thia-hexanedioate of di3-benzylthiopropylammonium having the formula:

(2-benzylthio-ethylammonium) having the formula:

It is soluble in water, insoluble in ethanol and in other ordinarysolvents but soluble in hot methanol.

HO C-CH- H -s- 2 c 2 CH2 002K,

I In the same manner as in Example 1, 8.9 g of S- O.l mol of2-benzylth1o ethylamme is added drop by carboxymethy] cysteine arereacted with 91 g of drop to a conical 100 cm flask containing 0.05 molof 5-acetamido-3-thia-hexanedioic acid in solution in 30 cm of absoluteethanol. The reaction mixture is then left to stand overnight at l5C.

benzylthio-propylamine in ethanol.

It is soluble in water and, when hot, in ethanol.

The result is 16.5 g of a white solid melting at 129C.

40 5-acetamido-3-thia-hexanedioate of di (2-benzylthio ethylammonium)crystallizes out in the form of fine EXAMPLE 6 needles, which arefiltered out, washed in absolute Preparation of 2-amino-4-thiaheptanedioate of ethyl alcohol, and vacuum dried in the presence of2-benzylthio-ethylammonium having the formula: phosphoric anhydride.

The yeidl of yield reaction is 65 The resulting product is in the formof white needles HO C-CH-CH -S-CH -CH -CO H, having a melting point of120C. 2 2 2 2 2 It is insoluble in ethanol, but very soluble in water Hand in a mixture of water and ethyl alcohol. 5

EXAMPLE 3 H N-CH -Cl-l -S-CH -C H Preparation of 5-amino-3-thiahexanedioate of In the same manfler as in Example 1, g of 2 (3a1any1thio) ethylammonium having to the carboxyethyl cysteine arereacted with 33.4 g of 2- f l benzylthio-ethylamine in ethanol.

HO2C-JCH-CH2 SFCHQ-CO2H, H N-Cl-l -CH -S-Cl-I Ci1H-NH 16.4 g of3-(2-aminoethylthio) alanine are dissolved The result is 60.5 g of awhite solid melting at 95C, in a mixture of 250 cc of methanol and 50 ccof water. soluble in water and insoluble in alcohols. Into thissolution, vigorously agitated and heated to reflux there are added 17.9g of S-carboxymethyl- EXAMPLE 7 cysteine, little by little. The saltprecipitates, and the Preparation of 5-amino-3-thia hexanedioate ofprecipitate is filtered, washed with absolute methanol,2-(2,2-dimeth0Xy-ethyhhi0)-ethylamm0nium, having and dried. The yield isthe formula:

EXAMPLE 8 Preparation of 2-acetamido-3-benzylthiopropionate of2-methylthioethylammonium having the formula:

In the same manner as in Example 2, 25.3 g of N- acetyl S-benzyll-cysteine are reacted with 9.1 g of 2- methylthio-ethylamine inethanol.

The result is 24 g of a product in the form of white needles, whichmelts at 131C and is soluble in water and alcohol.

Active compounds Nos. 9-65 listed above are prepared in a manneressentially as described in Example 2, employing corresponding amountsof the appropriate cysteamine derivative for the 2-benzylthio ethylamineand of the appropriate cysteine derivative for the 5-acetamido-3-thiahexanedioic acid of Example 2.

The compounds of the present invention can advantageously beincorporated into both topically applied and orally administeredcompositions for use by persons having a scalp or skin characterized byan excessive secretion of sebum to reduce or diminish said excessivesecretion.

II. Topically Applied Compositions In accordance with the presentinvention, there is provided a variety of compositions which can betopically applied to the scalp or skin to achieve the aforementionedresult and these compositions can include dermal preparations which canbe in the form, for instance, of a cream, milk, lotion, gel, cake oraerosol. The active ingredient of this invention is present in thesetopically applied compositions in amounts of about 0.1-5 percent,preferably about 0.75-3 percent, by weight of the total composition.Generally, these compositions have a pH ranging from about 3 to 13 andare solutions of the active ingredient in water, a lower alkanol oraqueous solutions of a lower alkanol wherein the lower alkanol ispresent in amounts of about 20 to 70 weight percent of said aqueoussolutions. The choice of solvent for the active ingredient can depend ona number of easily ascertainable factors such as the particular activeingredient chosen, its solubility characteristics, the ultimate use ofthe composition and the like. When a lower alkanol, alone or as anaqueous solution thereof, is selected, generally the alkanol is ethanolor isopropanol. In addition to the solvent, the activeingredient-containing composition can also be formulated withconventional adjuvants such as emulsifiers,

preservatives, perfumes, dyes, emollients, waxes, pigments, detergentscationic, anionic, nonionic and amphoteric, thickeners, oils and thelike.

When the topically applied compositions of the present invention areemployed in aerosol form, generally the active ingredient is present asa solution thereof in a lower alkanol, together with a conventionalaerosol propellant such as a fluorinated hydrocarbon such asdichlorodifluoromethane, trichloromonofluoromethane and mixturesthereof. Obviously, other well-known propellants can also be used.Generally, the propellant is present in amounts of about 66 to 75 weightpercent of the total aerosol composition, which is, of course, packagedunder pressure.

The topically applied compositions also include hair setting lotion andlacquer formulations. Again, the active compound of this invention ispresent in such formulations in amounts ranging from about 0.1-5 percentby weight of said formulation, and is present as a solution thereof inwater, lower alkanol or mixtures thereof as defined above. Additionallysuch hair setting lotions and lacquers also include, advantageously, afilm-forming resin having a molecular weight ranging from about 10,000to 3,000,000. Typical film forming resins include polyvinyl pyrrolidonehaving a molecular weight of about 10,000-700,000; copolymers ofpolyvinyl pyrrolidone and vinyl acetate wherein the ratio of VP to VAcan range between :30 to 30:70 and which have a K value (1% ethanolsolution) of about 20-50; copolymers of vinyl acetate, crotonic acid andan acrylic or methacrylip ester; copolymers of vinyl acetate and a vinylalkyl ether; copolymers of vinyl acetate, crotonic acid and a vinylester of a long carbon- 7 chain acid or an ally] or methallyl ester of along carbon-chain acid; copolymers of an ester of an unsaturated alcoholand a short chain carboxylic acid, a short carbon-chain unsaturated acidat at least one ester derived from a short chain saturated alcohol andan unsaturated acid; and copolymers of and least one unsaturated esterand at least one unsaturated acid. A specific vinyl acetate/crotonicacid copolymer usefully employed is that sold under the trade name RESYN28,1310 having a molecular weight of 20,000. Other resins usefullyemployed are those sold under the trade name GANTREZ including GANTREZAN 3953 which is the half butyl ester of GANTREZ AN 119 which ismethylvinylether/maleic anhydride copolymer having a specific viscosityof 0.1-0.5 in a 1% solution of the copolymer in methylethyl ketone at25C.

The hair setting and lacquer formulations can also be packaged inaerosol form using the aerosol propellants and the amounts thereof asdescribed above.

Yet another topically applied composition according to the invention isa shampoo formulation which also contains the active ingredient inamounts of about 0.l5 percent by weight. Again, the carrier for saidactive compound can be water of an aqueous solution of a lower alkanolas described above. In addition, these shampoo compositions which have apH of about 3-8 also contain about 5-60% of an anionic, amphoteric,cationic or nonionic detergent.

Anionic detergents include both the soap and nonsoap detergents.Examples of suitable soaps are the sodium, potassium, ammonium andalkanol ammonium salts of higher fatty acids (Cg-C20). Examples ofanionic non-soap detergents are alkyl glyceryl ether sulfonates, alkylsulfates, alkyl ether sulfates, alkyl sulfonates, alkyl monoglyceridesulfates or sulfonates, alkyl polyethoxy ether sulfates, alkanolamidesulfonates, alkanolamide sulfates, alkyl monosulfosuccinates, acylsarcosinates, acyl esters of isethionates, acyl-N-methyl taurines, alkylbenzene sulfonates and alkyl phenol polyethoxy sulfonates. In thesecompounds the alkyl and acyl moieties, respectively, can contain 8-20carbon atoms and they can be used in the form of watersoluble salts suchas the sodium, potassium, ammonium and alkanol ammonium salts.

Suitable examples of cationic detergents are dilauryldimethyl ammoniumchloride, diisobutyl phenoxy ethoxy ethyl dimethylbenzyl ammoniumchloride, cetyl trimethyl ammonium bromide, N-cetyl pyridinium bromideand benzethonium chloride, lauryl benzyl trimethyl ammonium bromide orchloride, myristyl benzyl trimethyl ammonium bromide or chloride andcetyl benzyl trimethyl ammonium bromide or chloride.

Suitable examples of amphoteric detergents are aspargine derivatives,alkyl dimethyl betaine, alkyl betaamino propionates wherein the alkylmoiety contains 10-20 carbon atoms, basic quaternary ammonium compoundsderived from 2-alkyl-substituted imidazoline and compounds having theformula R-NH-CH-COONa. C H

CH2-CONH-(CH2)3 N\ wherein R is a radical derived from fatty acids ofcopra and radicals (C to C derived from tallow.

Representative nonionic detergents are ethylene oxide adducts of fattyalcohols, long chain phenols (e.g. octadecyl phenol), long chainmercaptans or long chain amides, such as lauryl alcohol oxyethylenatedwith 12 moles ethylene oxide and C thiols oxyethylenated with 12 molesof ethylene oxide.

The shampoo formulations can, of course, contain any of the usualshampoo additives such as color, per- 5 aminophenol,

phenylene diamine, nitro-meta phenylene diamine,

meta toluylene diamine, 2,4-diamino anisol sulfate, meta amino phenol,3,5-diamino phenol hydrochloride, diethyl meta aminophenol, paraaminoortho cresol, 1- hydroxy-2,4-di-(p-trimethylammonium- 5phenylamino)anthraquinone methosulfate, l-hydroxy-2,4-di(p-trimethylammonium phenylamino) anthraquinone iodide,l-aminopropylamino anthraquinone, and N-y-amino propylamino-4 andN'-methyl-amino-l anthraquinone. Additional examples of commerciallyavailable useful dyes include, as monoazo dyes, Cl Acid Blue 92 (13390),Cl Acid Yellow 23 (19140); as diazo dyes, Cl Acid Orange 24 (20170); astriphenylmethane type dyes, Cl Acid Blue 1 (42045), CI Acid Violet 19(42685), CI Acid Blue 22 (42755), CI Acid Violet 15 25 43525 as xanthenedyes, (:1 Acid Violet 9 45190 as azine dyes, Cl Acid Black 2 (50420), ClAcid Blue 59 (50315), CI Acid Blue 61 (50330), as anthraquinone dyes, CIAcid Violet 43 (60730), Cl Acid Blue 80 (61585), Cl Acid Violet 51(62165), CI Acid Blue 138 (62075); as premetallized dyes, both 1:1 and2:1 complexes-chromium and cobalt, for instance, Cl Acid Black 43 (15691as disperse dyes, CI Disperse Blue 14 (61500), Cl Disperse Blue 6(62050), CI Disperse Blue 31 (64505); as direct dyes, CI Direct Blue 235 22590 or Direct Black 51 27720 or Direct Violet 51 (27905 and assolvent dyes, CI. 15680 and Cl Solvent Violet 10 (45190).

Yet another topically applied composition including the active compoundsof the present invention is a formulation for use in effecting apermanent wave or deformation of oily hair.

In one embodiment of the use of such permanent wave formulations, thehair is permanently waved by applying to the hair wound on curlersduring the first stage, i.e., during the reducing stage, a cosmeticcomposition comprising a mixture of a reducing agent and the activecompound of this invention as defined above, permitting the compositionto remain on the fume, thickeners, solvents, opacifiers, suds builders,hair for a time sufficient to alter the disulphide bonds conditioningagents, preservatives, buffers and antistatic agents. Generally 10-20 cmof the shampoo composition applied to the scalp and hair once a week forabout 4 weeks provides desirable results.

Still further topically applied compositions according 55 to the presentinvention include hair -aminophenol, compositions for coloring humanhair. These compositions contain the active compound of this inventionin the aforesaid quantities and in an aqueous or aqueous of the keratinof the hair, generally about 10 to 40 minutes, thoroughly rinsing thehair toremove residual reducing agent and applying in the second stage,i.e., during the neutralization stage, an oxidizing or neutralizingagent to reform the disulphide bonds of the keratin of the hair.

In another embodiment of using these permanent wave formulations thehair is permanently waved by Y applying to the hair wound on curlersduring the first alkanol solution as described above. Conventional hairstage, i.e., during the reducing stage, a reducing agent,

dyes, such as azo, anthraquinone and nitro dyes of the benzene seriescan be used in such compositions in amounts sufficient to color thehair. Representative dyes include paraphenylene diamine, 2,5-toluenediamine sulfate, chloroparaphenylene diamine sulfate,

nitroparaphenylene diamine, 1,2,4-triamino benzene dihydrochloride,paraaminodiphenyl amine, ortho phenylene diamine, 4-chloro orthophenylene diamine,

permitting the composition to remain on the hair for a time sufficientto alter the disulphide bonds-of the keratin of the hair, generallyabout 10 to 40 minutes, thoroughly rinsing the hair to remove residualreducing agent and applying in the second stage, i.e., during theneutralization stage, a cosmetic composition comprising a mixture of anoxidizing or neutralizing agent and the active compound as definedhereinbefore whereby the disulphide bonds of the keratin of the hair arereformed.

In an alternative procedure the hair is permanently waved byimpregnating the hair wound on curlers with a cosmetic compositioncomprising a mixture of a thiol reducing agent for altering thedisulphide bonds of the keratin of the hair, an organic disulphide andthe active compound of the present invention, the molar ratio of saidorganic disulphide to said thiol being greater than 1, and as high asabout 20, permitting the composition to remain on the hair for a timesufficient to induce a permanent wave therein, generally about to 40minutes, and unwinding the hair from the curlers, Conventional separateneutralization operations are not required in the practice of thisembodiment of the invention.

The active compound of this invention used in these permanent waveformulations is admixed with a conventional reducing agent and ispresent in the resulting mixture in amounts between 0.1 to 5 percent byweight of the total and preferably between 1 and 3 weight percent. ThepH of this cosmetic composition is preferably between 3 and 9.5.Conventional reducing agents employed are advantageously those organicthiols which are generally used to perform the first stage of apermanent waving operation. Representative thiols include thioglycolicacid, ammonium thioglycolate, thioglycerol, thiolactic acid,thioglycolic amide or hydrazide or the like.

Conveniently, and also in accordance with the present invention, thereducing composition is a twopackage composition, the first packagecontaining a thiol reducing agent as described above and the secondpackage containing the active compound of this invention in amounts suchthat when the contents of two packages are mixed together, preferablyjust before initiation of the reducing operation, the resulting reducingcomposition contains said active compound in amounts of about 0.1-5weight percent of the total mixture.

Alternatively, the said active compound is admixed with a conventionalneutralizing or oxidizing agent and is present in the resulting mixturein amounts between 0.1 to 5 weight percent, and preferably between about1 and 3 weight percent of the total. Conventional neutralizing agentsemployed include, for instance, hydrogen peroxide, sodium or potassiumbromate, sodium perborate or percarbonate and the like.

Conveniently also, the neutralizing composition is a two-packagecomposition, the first package containing the neutralizing agent asdescribed above and the second package containing said active compoundalso as defined above in amounts such that when the contents of the twopackages are mixed together, preferably just before initiation of theneutralizing operation, the resulting neutralizing composition containsthe active compound in amounts of about 0.1-5 weight percent of thetotal mixture.

As a further alternative, the active compound is admixed with a singlestage permanent hair waving agent, and is present in the resultingmixture in amounts between O.1-5 weight percent, and preferably, betweenabout 1 and 3 weight percent of the total. Conventional single stagepermanent hair waving agents can be employed and include a mixture of anorganic disuifide and a thiol, the mol ratio of the disuliide to thethioi being greater than 1.

Suitable thiols include thioglycolic acid, glycol thioglycolate,glycerol thioglycolate, B-mercaptoethanol,

N-carboxymethyl-mercaptoacetarnide, glycol thiolactate and the like.

As the organic disulphides there can be used the disulphides of thethiols set forth in the preceding paragraph. For instance, glycoldithiodiglycolate, glycerol dithioglycolate, glycol dithiodilactate,dithiodiethanol and N-carboxymethyldithioacetamide can be employed.Additional ingredients can include ammonia, water, urea and loweralkanols in conventionally employed amounts and the pH of the singlestage permanent hair waving agent ranges between about 8-10, preferablyabout 8.5-9.5. Typical formulations of such single stage permanent hairwaving agents are disclosed in French Pat. Nos. 1,443,888 and 4,455,788.

Again, conveniently, the single stage permanent hair waving compositionis a two-package composition, the first package containing the singlestage permanent hair waving agent and the second package containing theactive compound, as defined above, in amounts such that when thecontents of the two packages are mixed together, preferably just beforeuse, the resulting permanent hair waving composition contains the activecompounds in amounts of about 0. l-5 weight percent of the totalmixture.

As will be recognized, these permanent wave formulations can alsoinclude other additives conventionally employed such as penetratingagents, surfactants, dyes or perfumes and can be admixed withconventional vehicles such as water, lower alkanols and their mixturesas defined above. Further, they can also be provided in the form of asolution, a foam, a cream or gel or can be provided in the form of asprayable aerosol especially when the cosmetic vehicle is water, loweralkanol or their mixtures. The sprayable aerosol can include an amountof a liquefied gas under pressure, such as a fluorochlorinatedhydrocarbon, also as defined hereinbefore.

in yet another embodiment of the present invention, a dermal lotioncomposition can be prepared which contains as the active ingredient thecompound defined above present in amounts of about 0.1-3 percent byweight of said composition. Additionally, where the active compoundcomprises a free carboxylic acid group, this can take the form of acomplex with a cationic quaternary ammonium bactericide, such as(diisobutyiphenoxyethoxyethyl dimethyl benzyl) ammonium chloridemonohydrate or (diisobutyl cresoxyethoxyethyl dimethyl benzyl) ammoniumchloride monohydrate.

lll. Orally Administered Compositions in accordance with anotherembodiment of the present invention, there is provided a composition andmethod for treating a scalp characterized by an excessive secretion ofsebum, to improve the condition thereof by reducing said excessivesecretion which comprises orally administering to a human being having ascalp so characterized a therapeutic composition comprising aningestible carrier admixed with, as a non-toxic active ingredient, anactive compound as defined hereinbefore.

These novel compositions can be in liquid or solid form and when theliquid form is desired, the active compound can be dissolved in analimentary liquid, such as water or an aqueous solution of a non-toxiclower alcohol, such as ethanol. These liquid orally administeredcompositions generally contain about l-l .5 percent by weight of theactive compound, the remainder being essentially the ingestible carrier.

The orally administered compositions can also be provided as a solid, inthe form of granules, pills, tablets and the like, and in this form theactive compound is generally present in amounts of about 0.75-20 weightpercent of the composition. Examples of suitable excipient or carrierformulations can be found in US. Pat. No. 2,888,380.

These compositions, whether in liquid or solid form, can be orallyadministered at a rate of about l-S mg/kg/day based on the weight of thehuman being,

and they are generally administered during a period of 15 about 15 days.After 15 days, the treatment may be stopped and then resumed 15 dayslater.

IV. Examples of Topically Applied Compositions EXAMPLE 9 A shampoohaving the following composition is prepared:

Technical (l%) triethanolamine lauryl sulfate 4 g Lauryl diethanolamide2 g 5-amino-3-thia hexanedioate of Z-benzylthioethylammonium l gCarboxymethylcellulose 0.2 g Perfume, phenilic alcohol, benzyl acetate,etc. 0.3 g Water, q.s.p. 100 g EXAMPLE A shampoo having the followingcomposition is prepared:

Technical (100%) alkyl sodium sulfate 0 E Pure mono lauryl sodiumsulfosuccinate Polyethylene glycol distearate Lauryl diethanolamide5-amino-3-thia hexanedioate of 2-benzylthioethylammonium Perfume,Patchoulis or rose extracts Lactic acid, q.s.p. pH 6.5

Water, q.s.p.

EXAMPLE 1 l A shampoo having the following composition is prepared:

100 alkyl sodium sulfate paste g Condensation product of fatty acids ofcopra and methyltaurine, a paste sold under the trademark Hostapon C.T.by

the Hoechst Co. 40 g Lauryl monoethanolamide 3 g Glycerol monostearate 2g 5-amino-3-thia hexanedioate of Z-benzylthioethylammonium l g Lacticacid, q.s.p. pH 6.6

Perfume, phenilic alcohol or natural extracts 0.4 g Water, q.s.p. 100 gEXAMPLE 12 A shampoo having the following composition is prepared:

Alkyl sodium sulfate powder 54 g Product of the condensation of thefatty acids of copra with sodium -Continued isethionate sold under thetrademark Hostapon K.A." by the Hoechst Co. 40 g 5-amino-3-thiahexanedioate of 2-benzylthioethylammonium 5 g 5 Perfume, like cinnamicalcohol or natural extracts l g EXAMPLE 13 A shampoo according to thepresent invention is pre- 0 pared as follows:

Technical triethanolamine lauryl sulfate Lauryl diethanolamide5-amino-3-thia hexanedioate of 2-(o-chlorobenzylthio) ethylammoniumCarboxymethylcellulose Perfume, phenilic alcohol, benzyl acetate, etc.

Water, q.s.p.

EXAMPLE 14 A shampoo having the following composition is prepared:

Technical (100 alkyl sodium sulfate O.E. Pure mono lauryl sodiumsulfosuccinate Polyethylene glycol distearate Lauryl diethanolamide5-amino-3-thia hexanedioate of Z-(p-bromobenzylthio) ethylammoniumPerfume, Patchoulis or rose extracts, etc. Lactic acid, q.s.p. PH 6.5

Water, q.s.p

EXAMPLE 15 A shampoo having the following composition is prepared:

EXAMPLE 16 A shampoo having the following composition is prepared:

Alkyl sodium sulfate powder 54 g Product of the condensation of thefatty acids of copra with sodium isethionate sold under the tradenameHostapon K.A." 40 g 5-amino-3-thia hexanedioate of 3-benzylthiopropylammonium 5 Perfume (cinnamic alcohol or naturalextracts) 1 EXAMPLE 17 The following hair waving reducing composition isprepared:

Ammonium thioglycolate 9.5 g

-Continued Fatty alcohol polyethoxy-ester (Cetyl alcohol 30 stearylalcohol 70 sold under the tradename Sipol Wax A 0.8 g Ammonia solution,q.s.p. 0.7 N

-amino-3-thia hexanedioate of 2- phenylthioethylammonium l g Water,q.s.p. 100 g After shampooing and drying, the hair is wound on curlersand is impregnated with the above composition. The composition isallowed to act for to 30 minutes. Thereafter, the hair is thoroughlyrinsed and there is then applied to the hair a neutralizing compositioncomprising a 6-volume hydrogen peroxide solution. The curlers areremoved and the hair is rinsed and dried. The hair thus permanentlywaved in accordance with this invention exhibited a non-oily appearancefor a significantly longer time than did the hair when permanently wavedusing essentially the same cosmetic composition but without5-amino-3-thia hexanedioate of Z-phenylthio-ethylammonium.

EXAMPLE 18 The first stage, i.e., the reducing stage, of a permanentwaving operation is performed with a reducing composition containing:

A two-package neutralizing composition is then employed, the firstpackage containing:

Hydrogen peroxide, q.s.p. 6.6 volumes Citric acid 0.] g Water, q.s.p.100 g and the second package containing:

5-amino-3-thia hexanedioate of 3- benzylthiopropylammonium l gImmediately prior to initiating the second stage of the permanent wavingoperation, i.e., the neutralizing stage, the powdered 5-amino-3-thiahexanedioate of 3-benzylthio-propylammonium is dissolved in the hydrogenperoxide solution and the hair previously treated with the abovereducing agent, being soft and pliable and still wound on curlers, istreated with the resulting neutralizing solution for a time sufficientto reform the disulphide bonds in the keratin of the hair.

After the hair has been rinsed, unwound from the curlers, and dried, apermanent wave is obtained which exhibits good holding characteristics.Equally important, however, is that the hair remained non-oily inappearance for a significantly longer time than did the hair whenpermanently waved using essentially the same neutralizing compositionbut without compound of the invention.

EXAMPLE 19 A composition according to the invention is prepared bydissolving 1.5 g of 5-amino3-thia hexanedioate of 2-(p-phenylbenzylthio)ethylammonium in 100 cc of perfumed distilled water.

EXAMPLE 20 A composition in accordance with the invention is obtained bydissolving 0.75 g of 5-amino-3-thia hexanedioate of 2-octadecylthioethylammonium in 100 cc. of

5 a 50% ethanolic aqueous solution.

EXAMPLE 21 A composition in accordance with the invention is prepared bydissolving 2 g of Z-hexaneamido 10 di-(p-methoxyphenyl)-3-methylthiopropionate of 2-(2,3-dihydroxypropylthio) ethylammonium in 100 cc ofa 20 ethanolic aqueous solution.

EXAMPLE 22 15 A grooming lotion for gentlemen is prepared by mixing:

3-methylthio-Z-trifluoroacetamido propionate of 2-oleylthio ethyl 2ammonium O Dimethylhydantoin formaldehyde resin 0Dimethyldilaurylammonium chloride 0. Perfume 0 Ethanol 5 Water, q.s.p. l

EXAMPLE 23 A grooming liquid gel is prepared by mixing:

3O 3-benzylthio-2'glutamino propionate of Z-tetrahydrofurfurylthioethylammonium Carboxyvinylpolymer-carboxypolymethylene, sold under thetrade name Carbopol 940" Polyvinylpyrrolidone (M.W. 40000) Lanolinoxyethylenated with 16 moles ethylene oxide.

Polyethyleneglycol (M.W. 300) Methylparahydroxybenzoate sold under thetrade name Nipagin M n-propyl-p-hydroxybenzoate, sold under the tradename Nipasol" Perfume Triethanolamine, q.s.p.

Water, q.s.p.

EXAMPLE 24 A cream for use on the face is prepared by mixing together:

2-0-chlorobenzylthiomethyl 3-aza- 4-oxo heptanedioate of 5,5 '-sulfonylCarboxyvinylpolymer-carboxypolymethylene,

EXAMPLE 26 A masking cream is prepared by mixing the followingingredients:

2-acetamido-3-( 3-alanylthio) propionate of 2-m'fluorobenzy1thioethylammonium Titanium oxide Red iron oxide Yellow iron oxide Brown ironoxide Chestnut iron oxide Cetyl stearyl alcohol oxyethylenated withmoles ethylene oxide Silicone oil (dimethyl polysiloxane having aviscosity of -22 degrees at room temperature) 1 g Polyglycol monostearate (m.w. polyglycolz400) 6 g Para-hydroxy acid ester 0.2 g

Water. q.s.p. 100 g EXAMPLE 27 A lotion is prepared by mixing thefollowing ingredients:

3-(3,4methylenedioxy benzylthio)-2-propionamido propionate of3-[2-(2,4-dihydroxy-3,3-dimethyl butyramido) ethylthiolpropylammoniumMonohydrate of (diisobutylphenoxyethoxyethyl-dimethyl-benzyl) ammoniumchloride 0 Perfume 0.

96 titer ethanol in water Water, q.s.p.

EXAMPLE 28 An aerosol foam is prepared by mixing the followingingredients in an aerosol bomb:

Carboxyvinylpolymer-carboxypolymethylene, sold under the trade nameCarbopol 934" 25 g Magnesium ethoxylauryl sulfate 8 g Glycerol 10 gAmmonia 0.2 g 5-tetradecanamido-3-thia hexanedioate ofdi-(Z-B-hydroxyethylthio ethylammonium) 2 g Water, q.s.p. 100 g 88 g ofthe above solution are packaged in an aerosol can with 12 g ofdifluorodichloromethane.

EXAMPLE 29 A thick hair lacquer of the following composition isprepared:

Vinylacetate-crotonic acid copolymer,

sold under the trade name Resin 28.1310 (m.w. about 20,000)

2-amino-2-methyl l-propanol -Continued 2-acetamido-3-p-fluorobenzylthiopropionate of 2-hexadecylthio ethylammonium 0.20 g

EXAMPLE 30 A dye setting lotion of the following formula is prepared andused for application on white hair having a greasy appearance:

Polyvinylpyrrolidone (P.V.P.)K value 30,

m.w. 4 0.4 g Vinylacetate-crotonic acid copolymer (resin 28.1310 ofNational Starch) (m.w. 20,000) 0.2 g Ethanol, q.s.p 50

2-butyramido-3-isopropylthio propionate of 2-(2,6-dichlorobenzylthio)ethylammonium 0 7 g 1-aminopropylaminoanthraquinone 0.03 g Picramic acid0.17 g n-oz-amino propylamino-4-N'-methylamino-1 anthraquinone 0.040 gWater g The pH value is adjusted to 7 by adding triethanolamine.

A good setting lotion is thus obtained which when applied on white hair,gives it a smoky gray shimmer while considerably improving its initialgreasy appearance.

EXAMPLE 31 A shampoo is made in accordance with the invention by mixing:

Technical (100%) triethanolamine lauryl sulfate Lauryl diethanolamide5-m-chlorobenzamido-3-thia hexanedioate of di-[2-(5-nitro-2-pyridylthio) ethylammonium] Carboxymethyl cellulose PerfumeWater, q.s.p.

EXAMPLE 32 Sodium lauryl sulfate oxyethylenated with 2.2 moles ofethylene oxide Pure mono lauryl sodium sulfosuccinate Lauryldiethanolamide Di-(S-amino-B-thia hexanedioate) of3-thia-1,-hexanediammonium Perfume Lactic acid, q.s.p. Water, q.s.p.

EXAMPLE 33 A shampoo cream in accordance with the invention is preparedas follows:

Sodium lauryl sulfate 12 g Product of the condensation of the fattyacids of copra with methyltaurine,

a paste sold under the trade name Hostapon CT." 40 g Laurylmonoethanolamide 2 g Glycerol monostearate 4 g 5amino-3-thiahexanedioate of 2- (3-methane sulfonamido propylthio) ethylammonium 3 gLactic acid, q.s.p. pH 6.5

Perfume 0.2 g Water, q.s.p. 100 g EXAMPLE 34 A shampoo powder inaccordance with the invention is prepared as follows:

EXAMPLE 35 A shampoo powder is prepared as follows: 1 5

Sodium lauryl sulfate powder 40 g Product of the condensation of fattyacids of copra with sodium isethionate, sold under the trade nameHostapon K.A. 29 g 2-butanesulfonamido-4-thia octanedioate of2,2'-(2,3-dihydroxyl ,4-butanediyl dithio) diethylammonium 20 g Perfumel g The powder of the two preceding examples can be dissolved in 10times its weight of water and the resulting solution applied to thehead.

EXAMPLE 36 A dye shampoo of the present invention is prepared asfollows:

di l 3-(2,2-ethylenedioxy ethylthio) 2-ureido propionate] of 2,2-thiodiethylammonium 5 g 3 5 Lauryl ammonium sulfate combined with Thisproduct is mixed with 1000 g of hydrogen peroxide at 20 volumes and haircontaining 80% white hair is impregnated therewith. A chestnut colorresults. The above shampoo composition has a pH range of 6.5 to 8.

EXAMPLE 37 The first stage, i.e., the reducing stage, of a pennanentwave operation is achieved by using a cosmetic composition containing:

Ammonium thioglycolate 9.5 g

Fatty alcohol polyethoxy-ester (cetyl alcohol 30%-stearyl alcohol 70%),sold under the trade name of Sipol Wax A0" 0.8 g Ammonia solution,q.s.p. 0.7 N

Water, q.s.p. l00 g Thereafter, the hair while still rolled on curlersis neutralized by applying to the same the following neutralizingcomposition:

Sodium bromate 18 g 2-amino4-thia nonanedioate of 2- -Continued(3-hydroxypropylthio) ethylammonium 0.5 g Water, q.s.p. 100 g Afterrinsing, the curlers are removed and the hair is then dried. A goodpermanent wave is obtained and the hair remained non-oily in appearancefor a significantly longer time than did the hair when permanently wavedusing a cosmetic composition essentially as described above but withoutany 2-amino-4-thia nonanedioate of 2-(3-hydroxypropylthio)ethylammonium.

EXAMPLE 3 8 The first stage, i.e., the reducing stage, of a permanentwaving operation is performed with a reducing composition containing:

Ammonium thioglycolate 9.5 g Fatty alcohol polyethoxy-ester (cetylalcohol 30% stearyl alcohol sold under the trade name of Sipol Ammoniasolution, q.s.p. Water, q.s.p.

A two package neutralizing composition is then employed, the firstpackage containing:

Hydrogen peroxide, q.s.p. 6.6 volumes Citric acid 0.1 g

Water, q.s.p.

and the second package containing:

S-amino-B-thia hexanedioate of 2-(3, 4-dichlorobenzylthio) ethylammoniumin powder form 5 g Immediately prior to initiating the second stage ofthe permanent waving operation, i.e., the neutralizing stage, thepowdered 5-amino-3-thia hexanedioate of 2-(3,4-dichloro benzylthio)ethylammonium is dissolved in the hydrogen peroxide solution. The hair,previously treated with the above reducing agent, being soft and pliableand still wound on curlers, is treated with the resulting neutralizingsolution for a time sufficient to reform the disulphide bonds in thekeratin of the hair.

After the hair has been rinsed, unwound from the curlers and dried, apermanent wave is obtained which exhibits good holding characteristics.Equally important, however, is that the hair remained non-oily inappearance for a significantly longer time than did the hair whenpermanently waved using essentially the same neutralizing compositionbut without the active compound.

V. EXAMPLES of Orally Administered Compositions.

EXAMPLES 39 49 2-amino-4-thia nonanedioate of 2- (3-hydroxypropylthio)ethylammonium l g Glycerin 40 g Ethyl alcohol 30 g Water, q.s.p. 100 gLemon tincture (q.s.p. imparts a pleasing aroma).

The oral administration of this composition at a rate of 10 drops eachday for 18 days by a person having greasy hair due to excessivesecretion of sebum substantially improve the condition of the scalp andthe appearance of the hair.

Essentially similar effective results are obtained when the above activecompound is replaced with the following compounds:

-amino-3-thia hexanedioate of 2-benzylthioethylammonium,5-acetamido-3-thia hexanedioate of di-( Z-benzylthioethylammonium),5-amino-3-thia hexanedioate of 2-(2-alanylthio) ethylammonium,S-amino-3-thia hexanedioate of 2-methylthioethylammonium, 5-amino-3-thiahexanedioate of 3-benzylthiopropylammonium, 2-amino-4-thia heptanedioateof 2-benzylthioethylammonium, 5-amino-3-thia hexanedioate ofdimethoxyethylthio)-ethylammonium, 2-acetamido-3-benzylthio propionate2-methylthioethylammonium, 5-benzamido-3-thia hexanedioatebenzylthioethylammonium), and 5-nicotinamido-3-thia hexanedioatebenzylthioethylammonium).

EXAMPLES 50 60 The following composition is prepared:

of di-(2- 5-amino-3-thia hexanedioate of 2-(6-methyl Z-pyridylthio)propylammonium Glucose Water, q.s.p.

Orange juice (q.s.p. to impart a pleasant aroma) 50 mg 300 mg 5 ml5-acetamido-3-thia hexanedioate of di 2-(2,4-

dichlorobenzylthio) ethylammonium, 2-acetamido-4-thia heptanedioate ofdi-( 2- methylthioethylammonium),

2-amino-4-thia decanedioate of 2-benzylthioethylammonium,

5-amino-3-thia hexanedioate of 2-benzylthio propylammonium,

5-amino-3-thia hexanedioate of 2-benzylthio 2- methylpropylammonium,5-amino-3-thia hexanedioate ethylammonium, and 5-amino-3-thiahexanedioate thylammonium.

of phenylthio-2- of Z-t-butylthioe- EXAMPLES 61-71 Lozenges for oralconsumption having the following composition are prepared:

5-amino-3-thia hexanedioate of 2-octadecyl thio ethylammonium mg Lactose300 mg Powdered gum arabic I00 mg Simple syrup, q.s.p. 500 mg Theselozenges, taken at a rate of 15 each day, by a person having greasy hairand scalp due to excessive secretion of sebum substantially improve thecondition of the scalp and the appearance of the hair by reducingexcessive secretion of sebum.

Essentially similar effective results are achieved by replacing the5-amino-3-thia acid hexanedioate of 2- octadecylthio ethylammonium bythe following compounds:

5-amino-3-thia hexanedioate of 2-tritylthioethylammonium,

5-amino-3-thia hexanedioate of 2-thenylthioethylammonium,

5-amino-3-thia hexanedioate pyridylmethylthio) ethylammonium,

5-amino-3-thia hexanedioate of 2-(2-pyridylthio N- oxide) ethylammonium,

5-amino-3-thia hexanedioate of 2-(2-butenylthio) ethylammonium,

5-amino-3-thia hexanedioate hydroxyethylthio)-ethylammonium,5-amino-3-thia hexanedioate of 2-(2,3-dihydroxypropylthio)ethylammonium, 3-benzylthio-2-phenylacetamido propionate2-methylthioethylammonium, 2-acetamido-3-tritylthiopropionate of2-methylthioethylammonium, and 2-acetamido-3-benzhydrylthio2-methylthioethylammonium.

propionate of EXAMPLES 72-82 Chewable pellets having the followingcomposition are prepared:

3-methylthio-2-trifluoroacetamido propionate of 2-oleylthioethylammonium 5 g Sucrose 200 g Lemon syrup 50 g These pellets,administered at the rate of a coffee spoonful twice a day for a periodof about 15 days to a person having greasy hair and scalp due toexcessive secretion of sebum substantially reduces excessive secretionof sebum and thereby significantly improves the condition of the scalpand the appearance of the hair.

Essentially similar effective results are achieved by p-acetamido-S--amino-3-thia hexanedioate of 2-octadecylthio ethylammonium,2-amino-4-thia heptanedioate of Z-undecenylthio ethylammonium, I2-amino-4-thia nonanedioate of 2-(3- hydroxypropylthio) ethylammonium,di-(5-amino 3-thia-hexanedioate) of 3thia-l,6-

hexanediammonium, 2-arnino-4-thia octanedioate of 2-(l3-ureidoethylthio)-ethylammonium,

5-amino-3-thia hexanedioate of 2-(3- methanesulfonamido propylthio)ethylammonium, and

2-amino-4-thia decanedioate of Z-thenylthio ethylammonium.

EXAMPLES 83-97 Tablets having the following composition are prepared:

2-butanesulfonamido-4-thia octanedioate of 2,2-(2,3-dihydroxy-l,4-butanediyl dithio) diethyL ammonium mg lactose 150 mggum arabic 100 mg starch, q.s.p. 500 mg These tablets, taken at a rateof 10 each day for days by a person having greasy hair and scalp becauseof excessive secretion of sebum effectively reduce excessive sebumsecretion and significantly improve the appearance of the hair and scalpcondition.

Essentially similar effective results are achieved when the activecompound is replaced by the following compounds:

5-amino-3-thia hexanedioate phenylbenzylthio) ethylammonium,

5-tetradecanamido-3-thia hexanedioate of di-(Z-B- hydroxyethylthioethylammonium), 2-crotonamido-4-thia heptanedioate tertiobutylthioethylammonium),

5-m-chlorobenzamido-3-thia hexanedioate of di-[Z- (S-nitroZ-pyridylthio) ethylammonium],

Z-butanesulfonamido 4-thia-octanedioate of 2,2-

(2,3-dihydroxy-l ,4-butanediyl dithio) diethylammonium,

2-formamido-3-(2-propyne ylthio) propionate of 3- (l-naphthylthio)propylammonium, 3-methylthio-2-trifluoracetamido propionate of 2-oleylthio ethylammonium, di-[3-(2,2-ethylenedioxy ethylthio) 2-ureidopropionate] of 2,2'-thio diethylammonium,

3-benzylthio- 2-glutamino propionate of 2-tetrahydrofurfurylthioethylammonium, 2-o-chlorobenzylthiornethyl-3-aza-4-oxo heptanedioate of5,5'-sulfonyl bis(3-thia pentylammonium),2-benzenesulfonamido-3-furfurylthio propionate of 2-(2,4-dichlorophenylthio) ethylammonium, 2-hexaneamidodi-(p-methoxyphenyl)-3-methylthio of 2-(pof di-(2- propionate of 2-(2,3-dihydroxy propylthio ethylammonium, 5-amino-3-thia hexanedioate of2-( ochlorobenzylthio) ethylammonium, and 5-amino-3-thia hexanedioate of2-( bromobenzylthio) ethylammonium. What is claimed is: l. A cosmeticcomposition for topical application to human scalp and skincharacterized by an excessive secretion of sebum to improve thecondition thereof by reducing said excessive secretion of sebumcomprising a solution in a solvent selected from the group consisting ofwater, lower alkanol and an aqueous solution of lower alkanol of 0.1 to5 percent by weight of an active compound selected from the groupconsisting of:

2-methylthioethylammonium, 5-benzamido-3-thia-hexanedioate ofdi(Z-benzylthioethylammonium),5-p-toluenesu1fonamido-3-thia-hexanedioate of di( 2-benzylthioethylammonium),5-p-acetamidobenzenesulfonamido-3-thiahexanedioate of di-(Z-benzylthioethylammonium 5-p-acetamidobenzamido-3-thia-hexanedioate of(2-benzylthioethylammonium), 2-acetamido-4-thia-heptanedioateylthio-ethylammonium),

of di(Z-meth- 2-amino-4-thia decanedioate of 2-benzylthioethylammonium,5-amino-3-thia hexanedioate of Z-benzylthiopropylammonium,

5-amino-3-thia hexanedioate methylpropylammonium,

5-amino-3-thia hexanedioate of Z-phenylthioethylammonium,

5-amino-3-thia hexanedioate of 2-t-butylthioethylammonium,

5-amino-3-thia hexanedioate of 2-tritylthioethylammonium,

5-amino-3-thia hexanedioate of 2-(2-butenylthio) ethylammonium,

5-amino-3-thia hexanedioate of 2-(2- hydroxyethylthio)-ethylammonium,5-amino-3-thia hexanedioate. of 2-(2,3dihydroxypropylthio)ethylammonium, 3-benzylthio-2-phenylacetamido 2-methylthioethylammonium,2-acetamido-3-tritylthiopropionate of Z-methylthioethylammonium,

propionate of 2-acetamido-3-benzhydrylthio propionate of2-methylthioethylammonium, 5-amino-3-thia hexanedioate of 6-methanesulfonamido-6-ethoxy carbonyl-4-thia hexylammonium,

2-acetamido-4-thia-nonanedioate of 2,2'-thio bis (ethylammonium),

di-(,B-benzylthioethylammonium) 5-p-acetamido-3- thia-hexanedioate,

5-amino-3-thia acid hexanedioate of 2-octadecylthio ethylammonium,

2-amino-4-thia heptanedioate of 2-undecenylthio ethylammoniurn,

of 2-benzylthio-2- I -amino-3-thia hexanedioate of 2-( 3methanesulfonamido propylthio) ethylammonium, 5-amino-3-thiahexanedioate of 2-(pof di(2- 2-acetamido-3-(3-alanylthio) propionate of2-mfluorobenzylthio ethylammonium, 6-amino-3-thia heptanedioate ofdimethylaminobenzylthio ethylammonium, 2-hexanamido-di-(p-methoxyphenyl)-3-methylthio propionate of 2-(2,3-dihydroxy propylthio)ethylammonium, 5-amino-3-thia hexanedioate of 2-(0- chlorobenzylthio)ethylammonium, 5-amino-3-thia hexanedioate of 2-(pbromobenzylthio)ethylammonium, 5-acetamido-3-thia hexanedioate of di-2-(2,4-

dichlorobenzylthio) ethylammonium, and

2-acetamido-3-p-fluorobenzylthio propionate of 2- hexadecylthioethylammonium.

2. The composition of claim 1 wherein said compound is S-amino 3-thiahexanedioate of 2-benzylthioethylammonium.

3. The composition of claim 1 wherein said active compound is present inamounts of 0.75-3 percent by weight of said composition.

4. A method for treating the scalp and skin, characterized by anexcessive secretion of sebum, to improve the condition thereof byreducing said excessive secretion os sebum comprising topically applyingto the scalp or skin of a human being having a scalp or skin socharacterized the composition of claim 1 in amounts effective to reduceexcessive secretion of sebum from said scalp or skin.

UNITED STATES PATENT OFFICE (IERTIFICATE OF CORRECTION Patent No.3,879,560 Dated April 2 1975 I Gregoire Kalopissis It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

In the Heading Under [30] Foreign Priority Data, change I Signed andScaled this eighth Day of June1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner nfPalemsand Trademarks

1. A COSMETIC COMPOSITION FOR TOPICAL APPLICATION TO HUMAN SCALP ANDSKIN CHARACTERIZED BY AN EXCESSIVE SECRETION OF SEBUM TO IMPROVE THECONDITION THEREOF BY REDUCING SAID EXCESSIVE SECRETION OF SEBUMCOMPRISING A SOLUTION IN A SOLVENT SELECTED FROM THE GROUP CONSISTING OFWATER, LOWER ALKANOL AND AN AQUEOUS SOLUTION OF LOWER ALKANOL OF 0.1 TO5 PERCENT BY WEIGHT OF AN ACTIVE COMPOUND SELECTED FROM THE GROUPCONSISTING OF: 5-AMINO-3-THIA HEXANEDIOATE OF 2BENZYLTHIOETHYLAMMONIUM,5-ACETAMIDO-3-THIA-HEXANEDIOTE OF DI(2-BENZYLTHIOETHYLAMMONIUM),5-AMINO-3-THIA HEXANEDIOATE OF 2-(3-ALANYTHIO) ETHYLAMMONIUM,5-AMINO-3-THIA HEXANEDIOATE OF 2METHYLTHIOETHYLAMMONIUM, 5-AMINO-3-THIAHEXANEDIOATE OF 3BENZYLTHIOPROPYLAMMONIUM, 2-AMINO-4-THIA HEPTANEDIOATEOF 2BENZYLTHIOETHYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2-(2,2,DIMETHOXYETHYLTHIO)-ETHYLAMMONIUM,2-ACETAMIDO-3-BENZYLTHIO-PROPIONATE OF 2METHYLTHIOETHAMMONIUM),5-BENZAMIDO-3-THIA-HEXANEDIOATE OF DI(2BENZYLTHIOETHYLAMMONIUM),5-P-TOLUENSULFONAMIDE-3-THIA-HEXANEDIOATE OFDI(2BENZYLTHIOETHYLAMMONIUM),5-P-ACETAMIDOBENZENESULFONAMIDO-3-THIA-HEXANEDIOATE OFDI-(2-BENZYLTHIOETHYLAMMONIUM),5-P-ACETAMIDOBENZAMIDO-3-THIA-HEXANEDIOATE OF DI(2BENZYLTHIOETHYLAMMONIUM), 2-ACETAMIDO-4-THIA-HEPTANEDIOATE OFDI(2-METHYLTHIOETHYLAMMONIUM), 2-AMINO-4-THIA DECANEDIOATE OF2BENZYLTHIOETHYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2BENZYLTHIOPROPYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2METHYLPROPYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2PHENYLTHIOETHYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2-TBUTYLTHIOETHYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2-TRITYLTHIOETHYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2-(2-BUTENYLTHIO) ETHYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2-(HYDROXYETHYLTHIO)ETHYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2-(2,3DIHYDROXYPROPYLTHIO) ETHYLAMMONIUM, 3-BENZYLTHIO-2-PHENYLACETAMIDOPROPIONATE OF 2METHYLTHIOETHYLAMMONIUM,2-ACETAMIDO-3-TRITYLTHIOPROPIONATE OF 2METHYLTHIOETHYLAMMONIUM,2-ACETAMIDO-3-BENZHYDRYLTHIO PROPIONATE OF 2METHYLTHIOETHYLAMMONIUM,5-AMINO-3-THIA HEXANEDIOATE OF 6-METHANESULFONAMIDE-6ETHOXYCARBONYL-4-THIA HEXYLAMMONIUM, 2-ACETAMIDO-4-THIA-NONANEDIOATE OF2,2''-THIO BIS (ETHYLAMMONIUM), DI-(B-BENZYLTHIOETHYLAMMONIUM)5-P-ACETAMIDO-3-THIAHEXANEDIOATE, 5-AMINO-3-THIA ACID HEXANEDIOATE OF2-OCTADECYLTHIO ETHYLAMMONIUM, 2-AMINO-4-THIA HEPTANEDIOATE OF2-UNDERCENYLTHIO ETHYLAMMONIUM, 2-AMINO-4-THIA NONADEODIATE OF2-(3-HYDROXYPROPYLTHIO) ETHYLAMMONIUM, DI-(5-AMINO-3-THIA HEXANEDIOATE)OF 3-THIA-1,6HEXANEDIAMMONIUM, 2-AMINO-4-THIA OCTANEDIOATE OF2-(B-UREIDO ETHYLTHIO)ETHYLAMMONIUM, 5-AMINO-3-THIA HEXANEDIOATE OF2-(3-METHANESULFONAMIDO PROPYLTHIO) ETHYLAMMONIUM, 5-AMINO-3-THIAHEXANEDIOATE OF 2-(P-PHENYLBENZYLTHIO) ETHYLAMMONIUM,5-TETRADECANAMIDO-THIA- HEXANEDIOATE OF DI(2-BHYDROXYETHYL THIOETHYLAMMONIUM), 2-CROTONAMIDO-4-THIA HEPTANEDIOATE OFDI(2-TERTIOBUTYLTHIO ETHYLAMMONIUM), 2-BUTANESULFONAMIDO-4-THIAOCTANEDIOATE OF 2,2''-(2,3DIHYDROXY-1,4-BUTANEDIYL DITHIO)DIETHYLAMMONIUM, 2-FORMAMIDO-3-(PROPYN-2-YLTHIO) PROPIONATE OF3-(1NAPTHYL THIO) PROPYLAMMONIUM, 3-METHYLTHIO-2-TRIFLUOROACETAMINOPROPIONATE OF 2OLEYLTHIO ETHYLAMMONIUM,2-O-CHLOROBENZYLTHIOMETHYL-3-AZA--4-OXO HEPTANEDIOATE OF 5,5''-SULFONYLBIS (3-THIA PENTYLAMMONIUM), 2-ACETAMINO-3-P-METHYLTHIOPHENYLTHIOPROPIONATE OF 2(2,4,6-TRIMETHYL BENZYLTHIO) ETHYLAMMONIUM,5-AMINO-3-THIA HEXANEDIOATE OF 2(3,4-DICHLOROBENZYLTHIO) ETHYLAMMONIUM,2-BUTYRAMIDO-3-ISOPROPYLTHIO PROPIONATE OF 2-(2,6-DICHLORO BENZYLTHIO)ETHYLAMMONIUM, 2-ACCTAMIDO-3-THIA HEPTANEDIOATE OF 2-PFLUOROBENZYLTHIOETHYLAMMONIUM, 6-AMINO-3-THIA HEPTANEDIOATE OF 2-PDIMETHYLAMINOBENYLTHIOETHYLAMMONIUM, 2-HEXANAMIDO-DI-(P-METHOXPHENYL)-3-METHYLTHIO PROPIONATEOF 2-(2,3-DIHYDROXY PROPYLTHIO) ETHYLAMMONIUM, 5-AMINO-3-THIAHEXANEDIOATE OF 2-(P-BROMOBENzYLTHIO) ETHYLAMMONIIUM, 5-AMINO-3-THIAHEXANEDIOATE OF 2-(P-BROMOBENXYLTHIO) -ETHYLAMMONIUM, 5-ACETAMIDO-3-THIAHEXANEDIOATE OF DI-2-(2,4DICHLOROBENZYLTHIO) ETHYLAMMONIUM, AND2-ACETAMIDO-3-P-FLUOROBENZYLTHIO PROPIONATE OF 2HEXADECYLTHIOETGHALAMMONIUM.
 1. A cosmetic composition for topical application tohuman scalp and skin characterized by an excessive secretion of sebum toimprove the condition thereof by reducing said excessive secretion ofsebum comprising a solution in a solvent selected from the groupconsisting of water, lower alkanol and an aqueous solution of loweralkanol of 0.1 to 5 percent by weight of an active compound selectedfrom the group consisting of: 5-amino-3-thia hexanedioate of2-benzylthioethylammonium, 5-acetamido-3-thia-hexanedioate ofdi(2-benzylthio-ethylammonium), 5-amino-3-thia hexanedioate of2-(3-alanylthio) ethylammonium, 5-amino-3-thia hexanedioate of2-metHylthioethylammonium, 5-amino-3-thia hexanedioate of3-benzylthiopropylammonium, 2-amino-4-thia heptanedioate of2-benzylthioethylammonium, 5-amino-3-thia hexanedioate of2-(2,2,-dimethoxyethylthio)-ethylammonium,2-acetamido-3-benzylthio-propionate of 2-methylthioethylammonium,5-benzamido-3-thia-hexanedioate of di(2-benzylthioethylammonium),5-p-toluenesulfonamido-3-thia-hexanedioate ofdi(2-benzylthioethylammonium),5-p-acetamidobenzenesulfonamido-3-thia-hexanedioate of di-(2-benzylthioethylammonium), 5-p-acetamidobenzamido-3-thia-hexanedioateof di- (2-benzylthioethylammonium), 2-acetamido-4-thia-heptanedioate ofdi(2-methylthio-ethylammonium), 2-amino-4-thia decanedioate of2-benzylthioethylammonium, 5-amino-3-thia hexanedioate of2-benzylthiopropylammonium, 5-amino-3-thia hexanedioate of2-benzylthio-2-methylpropylammonium, 5-amino-3-thia hexanedioate of2-phenylthioethylammonium, 5-amino-3-thia hexanedioate of2-t-butylthioethylammonium, 5-amino-3-thia hexanedioate of2-tritylthioethylammonium, 5-amino-3-thia hexanedioate of2-(2-butenylthio) ethylammonium, 5-amino-3-thia hexanedioate of2-(2-hydroxyethylthio)-ethylammonium, 5-amino-3-thia hexanedioate of2-(2,3-dihydroxypropylthio) ethylammonium,3-benzylthio-2-phenylacetamido propionate of 2-methylthioethylammonium,2-acetamido-3-tritylthiopropionate of 2-methylthioethylammonium,2-acetamido-3-benzhydrylthio propionate of 2-methylthioethylammonium,5-amino-3-thia hexanedioate of 6-methanesulfonamido-6-ethoxycarbonyl-4-thia hexylammonium, 2-acetamido-4-thia-nonanedioate of2,2''-thio bis (ethylammonium), di-( Beta -benzylthioethylammonium)5-p-acetamido-3-thia-hexanedioate, 5-amino-3-thia acid hexanedioate of2-octadecylthio ethylammonium, 2-amino-4-thia heptanedioate of2-undecenylthio ethylammonium, 2-amino-4-thia nonanedioate of2-(3-hydroxypropylthio) ethylammonium, di-(5-amino-3-thia hexanedioate)of 3-thia-1,6-hexanediammonium, 2-amino-4-thia octanedioate of 2-( Beta-ureido ethylthio)-ethylammonium, 5-amino-3-thia hexanedioate of2-(3-methanesulfonamido propylthio) ethylammonium, 5-amino-3-thiahexanedioate of 2-(p-phenylbenzylthio) ethylammonium,5-tetradecanamido-3-thia hexanedioate of di(2- Beta -hydroxyethyl thioethylammonium), 2-crotonamido-4-thia heptanedioate ofdi(2-tertiobutylthio ethylammonium), 2-butanesulfonamido-4-thiaoctanedioate of 2,2''-(2,3-dihydroxy-1,4-butanediyl dithio)diethylammonium, 2-formamido-3-(propyn-2-ylthio) propionate of3-(1-naphthyl thio) propylammonium, 3-methylthio-2-trifluoroacetamidopropionate of 2-oleylthio ethylammonium,2-o-chlorobenzylthiomethyl-3-aza-4-oxo heptanedioate of 5,5''-sulfonylbis (3-thia pentylammonium), 2-acetamido-3-p-methylthiophenylthiopropionate of 2-(2,4,6-trimethyl benzylthio) ethylammonium,5-amino-3-thia hexanedioate of 2-(3,4-dichlorobenzylthio) ethylammonium,2-butyramido-3-isopropylthio propionate of 2-(2,6-dichloro benzylthio)ethylammonium, 2-acetamido-3-(3-alanylthio) propionate of2-m-fluorobenzylthio ethYlammonium, 6-amino-3-thia heptanedioate of2-p-dimethylaminobenzylthio ethylammonium,2-hexanamido-di-(p-methoxyphenyl)-3-methylthio propionate of2-(2,3-dihydroxy propylthio) ethylammonium, 5-amino-3-thia hexanedioateof 2-(o-chlorobenzylthio) ethylammonium, 5-amino-3-thia hexanedioate of2-(p-bromobenzylthio) ethylammonium, 5-acetamido-3-thia hexanedioate ofdi-2-(2,4-dichlorobenzylthio) ethylammonium, and2-acetamido-3-p-fluorobenzylthio propionate of 2-hexadecylthioethylammonium.
 2. The composition of claim 1 wherein said compound is5-amino 3-thia hexanedioate of 2-benzylthio-ethylammonium.
 3. Thecomposition of claim 1 wherein said active compound is present inamounts of 0.75-3 percent by weight of said composition.